Printing inks and lacquers containing polyolefin waxes

ABSTRACT

Printing inks and paints comprising a polyolefin wax component prepared from one or more olefins by catalysis using a single-site catalyst based on a complex of a transition metal from groups 5 to 8 of the Periodic System of the Elements, which comprises not more than one cyclopentadienyl system per transition metal.

[0001] The present invention relates to printing inks and paintscomprising a polyolefin wax component prepared from one or more olefinsby catalysis using a single-site catalyst based on a complex of atransition metal from groups 5 to 8 of the Periodic System of theElements, which comprises not more than one cyclopentadienyl system pertransition metal. The present invention further relates to micronizedparticles of polyolefin waxes for use in the printing inks and paints ofthe invention, to a process for preparing printing inks and paints usingthe micronized polyolefin wax particles of the invention, and to amethod of printing paper or cardboard using the printing inks of theinvention.

[0002] Paints and printing inks are composed of a plurality ofconstituents.

[0003] The four principal constituents of printing inks are:

[0004] colorants, usually synthetic organic or inorganic pigments;examples are

[0005] inorganic pigments such as TiO₂, iron blue pigments or iron oxidepigments;

[0006] metal pigments such as bronzes, an example being aluminum powder(“silver bronze”), brass powder (“gold bronze”) or copper powder(“copper bronze”);

[0007] interference pigments, e.g., mother of pearl, pearl lustre;

[0008] pigmentary carbon black;

[0009] organic azo pigments, isoindoline pigments, phthalocyaninepigments or luminescent pigments;

[0010] fillers, examples being calcium carbonate, aluminum oxidehydrate, barium sulfate, silica, aluminum silicate (kaolin) or magnesiumsilicate (talc);

[0011] binders, selected from fatty, oxidatively drying or nondryingoils and—prepared from them—alkyd resins or solutions of resins;

[0012] solvents, such as water.

[0013] Furthermore, auxiliaries are incorporated as secondaryconstituents, examples being waxes, fatty acid amides, plasticizers,siccatives, and drying retardants.

[0014] Toners for copiers may be defined as special printing inks,comprising waxes not as a secondary constituent but instead as aprincipal component.

[0015] The effects of waxes in printing inks and paints are several:

[0016] they increase the abrasion, scratch and scuff resistance, i.e.,the mechanical properties of printed products;

[0017] in liquid paints, they act as rheological additives; i.e., theymay support the alignment of pigments, especially effect pigments, andmay control the settling behavior of pigments and fillers;

[0018] they may hydrophobicize the surfaces and so enhance the dirtrepellence;

[0019] they increase the lubricity of the printed surfaces and thus themechanical stability; for example, they reduce the formation of metalmarking tracks;

[0020] they increase the thermal load-bearing capacity; they can be usedto achieve dulling effects, by means of which it is possible to improve,for example, the readability of printed products even-under adverselight conditions (mirror effects).

[0021] So that waxes have the optimum morphology for paints and printinginks, they are preferably micronized, i.e., brought to the correctmorphology by grinding, spraying or (in the case of nonpolyethylenewaxes) by bead polymerization, by means of the chosen polymerizationtechnique. Micronized waxes are understood, accordingly, to be waxpowders having a maximum particle diameter of 30 μm.

[0022] It is important for the waxes used to possess a certain floatingcapacity, since this is prerequisite for optimum formation of slip,release and protective coats.

[0023] It is also a function of the waxes used to prevent the formationof large pigment agglomerates during the formulation process. Moreover,it is desirable to separate any agglomerated pigments formed beforehandand to split them into what are known as the primary particles. Finally,the primary particles should also remain separate after the formulationprocess and should not undergo reaggregation on cooling.

[0024] To this end, a number of requirements are imposed on the wax. Oneof these requirements concerns the viscosity of the melt. The meltviscosity should be as low as possible so that during the formulation,which usually takes place by mixing at a temperature above the meltingtemperature of the wax, the melted wax is able to penetrate effectivelythrough the cavities within the pigment agglomerates. As a result of theshear forces exerted in this way, the splitting of the agglomerates intothe primary particles takes place more readily.

[0025] The wetting ability of the waxes should also be good.

[0026] In principle, natural and synthetic waxes may be used. The mostsuitable waxes are polyolefin waxes. These may be obtained either byfree-radical polymerization of ethylene by the high pressure process(cf. Ullmann's Encyclopädie der technischen Chemie, 4th Edition, entry:Waxes, Vol. 24, p. 36 ff., Thieme Verlag Stuttgart, 1977) or byZiegler-Natta polymerization of ethylene or propylene (DE-A 15 20 914,EP-A 584 586). These methods allow polyolefin waxes to be obtainedhaving a broad molecular weight distribution and irregular incorporationof comonomers. The low molecular mass fractions which are present inthese products lead in most cases to reduced hardness of the finishedpaints or printing inks.

[0027] EP-A 890 619 discloses the use of waxes, preferably polyethylenewaxes, obtained by metallocene catalysis. They improve the hardness ofthe printing inks and paints prepared using them. For practicalpurposes, however, a further improvement is desirable. It is an objectof the present invention to provide such an improvement.

[0028] We have found that this object is achieved in that waxes preparedwith the aid of a complex of the formula I a to c are especiallysuitable as additives in printing inks and paints.

[0029] Waxes preparable with the aid of such single-site catalysts of atransition metal from groups 5 to 8 of the Periodic System whichcomprise not more than one cyclopentadienyl system per transition metalatom are known per se. The transition metal complexes required for thispurpose comprise compounds of the formula I a to c.

[0030] In formula I a

[0031] the variables are defined as follows:

[0032] M is an element from the group consisting of V, Nb, Ta, Cr, Mo,W, Mn, Fe in oxidation state +3; preferably V, Cr or Mo, and withparticular preference Cr;

[0033] X¹, X² are selected from

[0034] halogen such as fluorine, chlorine, bromine or iodine, chlorineand bromine being particularly preferred;

[0035] trifluoroacetate,

[0036] BF₄ ⁻, PF₆ ^(− or SbF) ₆ ⁻,

[0037] C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl, with particular preference C₁-C₄ alkylsuch as methyl, ethyl, n-propyl and n-butyl;

[0038] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptylare preferred,

[0039] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl,

[0040] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl;

[0041] C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, with particularpreference methoxy, ethoxy, n-propoxy and n-butoxy, or

[0042] NR⁸R⁹, where R⁸ and R⁹ independently of one another are selectedfrom hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl and C₆-C₁₄ aryl, which areable to form a saturated or unsaturated 5- to 10-membered ring;preference is given to the dimethylamino, the diethylamino, thediisopropylamino, the methylphenylamino and the diphenylamino groups.Examples of amino groups containing saturated rings are the N-piperidylgroup and the N-pyrrolidinyl group; examples of amino groups containingunsaturated rings are the N-pyrryl group, the N-indolyl group and theN-carbazolyl group.

[0043] Preferably, X¹ and X² are identical; with very particularpreference, X¹ and X² are chlorine.

[0044] R¹ to R⁶ independently of one another are

[0045] hydrogen,

[0046] halogen such as fluorine, chlorine, bromine or iodine, preferencebeing given to chlorine and bromine;

[0047] C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-Decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl, with particular preference C₁-C₄ alkylsuch as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl and tert-butyl,

[0048] C₁-C₁₂ alkyl substituted one or more times by donor atoms,examples being noncyclic or cyclic ethers, alcohols, ketals, thioethersor amines; specific examples are methoxymethyl, ethoxymethyl,ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,(2-ethylhexyloxy)propylidene, methoxyethoxypropylidene orω-dimethylaminopropyl;

[0049] mono- or polyhalogenated C₁-C₁₂ alkyl groups such asfluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl,particular preference being given to fluoromethyl, difluoromethyl,trifluoromethyl and perfluorobutyl;

[0050] C₂-C₁₂ alkenyl, preferably C₂ to ω-C₈ alkenyl such as vinyl,allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω-octenyl;

[0051] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0052] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl,

[0053] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl,

[0054] silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one anotherare selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyl, triethylsilyl,triisopropylsilyl, diethylisopropylsilyl, dimethylhexylsilyl,tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl,triphenylsilyl and the tri-para-xylylsilyl groups; particular preferenceis given to the trimethylsilyl group and the tert-butyldimethylsilylgroup;

[0055] siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² are selected independentlyof one another from hydrogen, C₁-C₁₋₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy,triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy,tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxygroups; particular preference is given to the trimethylsilyloxy groupand the tert-butyldimethylsilyloxy group;

[0056] C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, with particularpreference methoxy, ethoxy, n-propoxy and n-butoxy;

[0057] C₆-C₁₄ aryl substituted in turn by one or more C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹²,siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups specified as above;

[0058] A¹O—R¹³, S—R¹³, N(R¹³)₂ or P(R¹³)₂, R¹³ being selected fromhalogen, C₁-C₁₂ alkyl, C₂-C₁₂-alkenyl, C₃-C₁₂-cycloalkyl, substituted orunsubstituted C₆-C₁₄ aryl groups or C₁-C₁₂ alkoxy groups, these groupsbeing as defined for R¹ to R⁶.

[0059] In one particular embodiment of the present invention, twoadjacent radicals may together, with incorporation of the parentaromatic, form a 5- to 10-membered ring. For example, in formula I a, R³and R⁴ together may be: —(CH₂)₃— (trimethylene), —(CH₂)₄—(tetramethylene), —(CH₂)₅— (pentamethylene), —(CH₂)₆— (hexamethylene),—CH₂—CH═CH—, —CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—, —O—CH₂—O—, —O—CH(CH₃)—O—,—O—CH—(C₆H₅)—O—, —O—CH₂—CH₂—O—, —O—C(CH₃)₂—O—, —NCH₃—CH₂—CH₂—NCH₃—,—NCH₃—CH₂—NCH₃— or —O—Si(CH₃)₂—O—.

[0060] In another embodiment of the present invention, compounds of theformula I b are used as catalytically active components.

[0061] In formula I b, the variables are defined as follows:

[0062] Z¹ to Z⁴ independently of one another are

[0063] hydrogen,

[0064] halogen such as fluorine, chlorine, bromine or iodine, preferencebeing given to chlorine and bromine;

[0065] C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl, with particular preference C₁-C₄ alkylsuch as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl and tert-butyl,

[0066] C₁-C₁₂ alkyl substituted one or more times by donor atoms,examples being noncyclic or cyclic ethers, alcohols, ketals, thioethersor amines; specific examples are methoxymethyl, ethoxymethyl,ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,(2-ethylhexyloxy)propylidene, methoxyethoxypropylidene orω-dimethylaminopropyl;

[0067] mono- or polyhalogenated C₁-C₁₂ alkyl groups such asfluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl,with particular preference fluoromethyl, difluoromethyl, trifluoromethyland perfluorobutyl;

[0068] C₂-C₁₂ alkenyl, preferably C₂ to (O—C₈ alkenyl such as vinyl,allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω-octenyl;

[0069] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0070] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl,

[0071] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl,

[0072] silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one anotherare selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyl, triethylsilyl,triisopropylsilyl, diethylisopropylsilyl, dimethylhexylsilyl,tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl,triphenylsilyl and the tri-para-xylylsilyl groups; particular preferenceis given to the trimethylsilyl group and the tert-butyldimethylsilylgroup;

[0073] siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of oneanother are selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl andC₆-C₁₄ aryl; preference is given to the trimethylsilyloxy,triethylsilyloxy, triisopropylsilyloxy, diethylisopropylsilyloxy,dimethylthexylsilyloxy, tert-butyldimethylsilyloxy,tert-butyldiphenylsilyloxy, tribenzylsilyloxy, triphenylsilyloxy and thetri-para-xylylsilyloxy groups; particular preference is given to thetrimethylsilyloxy group and the tert-butyldimethylsilyloxy group;

[0074] C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, with particularpreference methoxy, ethoxy, n-propoxy and n-butoxy;

[0075] C₆-C₁₄ aryl, substituted in turn by one or more C₁-C₁₂ alkyl,C₁-C₁₋₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹²,siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups specified as above.

[0076] A² is selected from oxygen, sulfur, N—R¹³ and P—R¹³, preferablyN—R¹³ or P—R¹³, where R¹³ is as specified above.

[0077] In one particular embodiment of the present invention, twoadjacent radicals may together with one another and including the parentaromatic form a 5- to 10-membered ring. Thus in formula I b, forexample, R³ and R⁴ or Z¹ and Z² together may be: —(CH₂)₃—(trimethylene), —(CH₂)₄— (tetramethylene), —(CH₂)₅— (pentamethylene),—(CH₂)₆— (hexamethylene), —CH₂—CH═CH—, —CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—,—O—CH₂—O—, —O—CH(CH₃)—O—, —O—CH—(C₆H₅)—O—, —O—CH₂—CH₂—O—, —O—C(CH₃)₂—O—,—NCH₃—CH₂—CH₂—NCH₃—, —NCH₃—CH₂—NCH₃— or —O—Si(CH₃)₂—O—.

[0078] In a further particular embodiment, Z⁴ and A may together withone another and including the phenyl ring in formula I b form a 5- to10-membered ring. In a preferred embodiment, Z⁴ and A form, withinclusion of the phenyl ring, an indol system.

[0079] The other variables R¹ to R⁴, M, X¹ and X² are as defined forformula I a.

[0080] In formula I c

[0081] the variables are defined as follows:

[0082] X³, X⁴ and X⁵ independently of one another are

[0083] halogen such as fluorine, chlorine, bromine or iodine, chlorineand bromine being particularly preferred;

[0084] trifluoroacetate,

[0085] BF₄ ⁻, PF₆ ⁻ or SbF₆ ⁻,

[0086] c₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl, with particular preference C₁-C₄ alkylsuch as methyl, ethyl, n-propyl and n-butyl;

[0087] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; cyclopentyl, cyclohexyl and cycloheptylare preferred,

[0088] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl,

[0089] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl;

[0090] C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, with particularpreference methoxy, ethoxy, n-propoxy and n-butoxy, or

[0091] NR⁸R⁹, where R⁸ and R⁹ independently of one another are selectedfrom hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl and C₆-C₁₄ aryl, which areable to form a saturated or unsaturated 5- to 10-membered ring;preference is given to the dimethylamino, the diethylamino, thediisopropylamino, the methylphenylamino and the diphenylamino groups.Examples of amino groups containing saturated rings are the N-piperidylgroup and the N-pyrrolidinyl group; examples of amino groups containingunsaturated rings are the N-pyrryl group, the N-indolyl group and theN-carbazolyl group.

[0092] Preferably, X³ to X⁵ are identical; with very particularpreference, X³ to X⁵ are chlorine.

[0093] Nu¹ to Nu³ are selected independently of one another from N or P;preferably, Nu¹ and Nu² are each N, and with particular preference Nu¹to Nu³ are each N.

[0094] R¹⁴ to R¹⁶ independently of one another are

[0095] hydrogen,

[0096] halogen such as fluorine, chlorine, bromine or iodine, preferencebeing given to chlorine and bromine;

[0097] C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl, with particular preference C₁-C₄ alkylsuch as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl and tert-butyl,

[0098] C₁-C₁₂ alkyl substituted one or more times by donor atoms,examples being noncyclic or cyclic ethers, alcohols, ketals, thioethersor amines; specific examples are methoxymethyl, ethoxymethyl,ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,(2-ethylhexyloxy)propylidene, methoxyethoxypropylidene orω-dimethylaminopropyl;

[0099] mono- or polyhalogenated C₁-C₁₂ alkyl groups such asfluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl,particular preference being given to fluoromethyl, difluoromethyl,trifluoromethyl and perfluorobutyl;

[0100] C₂-C₁₂ alkenyl, preferably C₂ to ω-C₈ alkenyl such as vinyl,allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω-octenyl;

[0101] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0102] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl,

[0103] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl,

[0104] silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one anotherare selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyl, triethylsilyl,triisopropylsilyl, diethylisopropylsilyl, dimethylhexylsilyl,tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl,triphenylsilyl and the tri-para-xylylsilyl groups; particular preferenceis given to the trimethylsilyl group and the tert-butyldimethylsilylgroup;

[0105] siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² are selected independentlyof one another from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy,triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy,tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxygroups; particular preference is given to the trimethylsilyloxy groupand the tert-butyldimethylsilyloxy group;

[0106] C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, with particularpreference methoxy, ethoxy, n-propoxy and n-butoxy;

[0107] C₆-C₁₄ aryl substituted in turn by one or more C₁-C₁₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹²,siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups specified as above.

[0108] Preferably, R¹⁴ to R¹⁶ are identical.

[0109] R¹⁷ to R²² independently of one another are

[0110] hydrogen,

[0111] C₁-C₁₈ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl, with particular preference C₁-C₄ alkylsuch as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,sec-butyl and tert-butyl, mono- or polyhalogenated C₁-C₁₂ alkyl groupssuch as fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl,dichloromethyl, trichloromethyl, bromomethyl, dibromomethyl,tribromomethyl, pentafluoroethyl, perfluoropropyl and perfluorobutyl,particular preference being given to fluoromethyl, difluoromethyl,trifluoromethyl and perfluorobutyl;

[0112] C₁-C₁₂ alkyl substituted one or more times by donor atoms,examples being noncyclic or cyclic ethers, alcohols, ketals, thioethersor amines; specific examples are methoxymethyl, ethoxymethyl,ethoxyethyl, β-hydroxyethyl, ω-ethoxypropyl,(2-ethylhexyloxy)propylidene, methoxyethoxypropylidene orω-dimethylaminopropyl;

[0113] C₂-C₁₂ alkenyl, preferably C₂ to ω-C₈ alkenyl such as vinyl,allyl, but-3-en-1-yl, ω-pentenyl, ω-hexenyl, ω-heptenyl, and ω-octenyl;

[0114] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0115] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl,

[0116] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl,

[0117] silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one anotherare selected from hydrogen, C₁-C₁₋₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyl, triethylsilyl,triisopropylsilyl, diethylisopropylsilyl, dimethylhexylsilyl,tert-butyldimethylsilyl, tert-butyldiphenylsilyl, tribenzylsilyl,triphenylsilyl and the tri-para-xylylsilyl groups; particular preferenceis given to the trimethylsilyl group and the tert-butyldimethylsilylgroup;

[0118] siloxy OSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² are selected independentlyof one another from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; preference is given to the trimethylsilyloxy, triethylsilyloxy,triisopropylsilyloxy, diethylisopropylsilyloxy, dimethylthexylsilyloxy,tert-butyldimethylsilyloxy, tert-butyldiphenylsilyloxy,tribenzylsilyloxy, triphenylsilyloxy and the tri-para-xylylsilyloxygroups; particular preference is given to the trimethylsilyloxy groupand the tert-butyldimethylsilyloxy group;

[0119] C₁-C₁₂ alkoxy, preferably C₁-C₆ alkoxy such as methoxy, ethoxy,n-propoxy, iso-propoxy, n-butoxy, iso-butoxy, sec-butoxy, tert-butoxy,n-pentoxy, iso-pentoxy, n-hexoxy and iso-hexoxy, with particularpreference methoxy, ethoxy, n-propoxy and n-butoxy;

[0120] C₆-C₁₄ aryl substituted in turn by one or more Cl-C₁₋₂ alkyl,C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹²,siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups specified as above.

[0121] Preferably, R¹⁷, R¹⁹ and R²¹ are each identical, and preferablyR¹⁸, R²⁰ and R²² are each hydrogen. With very particular preference, R¹⁷to R²² are hydrogen. The triazacyclohexane ligands necessary forsynthesizing these very particularly preferred compounds may besynthesized with particular ease.

[0122] In one particular embodiment of the formula I c, two adjacentradicals may together form a saturated or unsaturated 4- to 9-memberedring; for example, two radicals may together be: C₃-C₉ alkylidene suchas, for example, —(CH₂)₃— (trimethylene), —(CH₂)₄— (tetramethylene),—(CH₂)₅— (pentamethylene), —(CH₂)₆— (hexamethylene), —CH₂—CH═CH—,—CH₂—CH═CH—CH₂—, —CH═CH—CH═CH—; and also cyclic aldols, ketals or aminessuch as, for example, —O—CH₂—O—, —O—CH(CH₃)—O—, —O—CH—(C₆H₅)—O—,—O—CH₂—CH₂—O—, —O—C(CH₃)₂—O—, —N(CH₃)—CH₂—CH₂—N(CH₃)—,—N(CH₃)—CH₂—N(CH₃)— or —O—Si(CH₃)₂—O—.

[0123] The other variables are as defined for formula I a.

[0124] The preparation of the transition metal complexes of the formulaI a to c is known per se. Suitable syntheses for complexes of theformula I a and b can be found in DE-A 197 10 615, in A. Döhring et al.,Organometallics 2000, 19, 388, and also in J. C. Weber, Dissertation,MPI Mulhouse/Ruhr, 1999.

[0125] The preparation of the particularly preferred triazacycloalkaneligands for complexes of the formula I c is known per se. Those for thesynthesis of the very particularly preferred compounds of the formula Ic where R¹⁷ to R²² are each hydrogen and the radicals R¹⁴ to R¹⁶ areeach identical may be synthesized very effectively by mixingformaldehyde in the form, for example, of formalin solution with theassociated amine R¹⁴—NH₂. Various synthesis pathways for these complexligands are described, for example, in F. Weitl et al., J. Am. Chem.Soc. 1979, 101 2728; M. Takahashi, S. Takamoto, Bull. Chem. Soc. Japan1977, 50, 3413; T. Arishima et al., Nippon Kagaku Kaishi 1973, 1119; L.Christiansen et al. Inorg. Chem. 1986, 25, 2813; L. R. Gahan et al.,Aust. J. Chem. 1982, 35, 1119; B. A. Sayer et al., Inorg. Chim. Acta,1983, 77, L63; K Wieghardt et al., Z. Naturforsch., 1983, 38b, 81 and I.A. Fallis et al., J. Chem. Soc., Chem. Commun. 1998, 665.

[0126] The metal complexes, especially the chromium complexes, may beobtained in a simple manner by reacting the corresponding metal saltssuch as metal chlorides or metal carbonyls, for example, with theligands, as for example in P. Chaudhuri, K. Wieghardt, Prog. Inorg.Chem. 1987, 35, 329 or G. P. Stahley et al., Acta Crystall. 1995, C51,18.

[0127] In order that above complexes of the formulae I a to c arecatalytically active, they are activated with a cation-forming compound.Suitable cation-forming compounds are selected aluminum or boroncompounds having electron withdrawing radicals (e.g.trispentafluorophenylborane, trispentafluorophenylaluminum,N,N-dimethylanilinium tetrakispentafluorophenylborate,tri-n-butylammonium tetrakispentafluorophenylborate,N,N-dimethylanilinium tetrakis(3,5-bisperfluoromethyl)phenylborate,tri-n-butylammonium tetrakis(3,5-bisperfluoromethyl)phenylborate, andtritylium tetrakispentafluorophenylborate). These activators forcomplexes of the formulae I a to c are described in DE-A 199 35 407, inPCT/EP 0002716, and in Angew. Chem. Int. Ed., 1994, Vol. 33, p. 1877.Preference is given to dimethylaniliniumtetrakispentafluorophenylborate, trityliumtetrakispentafluorophenylborate, and trispentafluorophenylborane.

[0128] Where boron or aluminum compounds are used as activators for thecomplexes of the formulae I a to c, they are generally employed in amolar ratio of from 1:10 to 10:1, based on M; preferably from 1:2 to 5:1and with particular preference from 1:1.5 to 1.5:1.

[0129] Another suitable class of cation-forming compounds comprises thealuminoxanes of the formulae II a and b.

[0130] The structure of the aluminoxanes is not precisely known. Theyare products obtained by careful partial hydrolysis of aluminum alkyls(see DE-A 30 07 725). These products do not exist in pure form but areinstead mixtures of open-chain and cyclic structures of type II a and b.These mixtures are presumed to exist in a dynamic equilibrium with oneanother.

[0131] In formulae II a and b, the radicals R²³ independently of oneanother are

[0132] C₁-C₁₂ alkyl such as methyl, ethyl, n-propyl, iso-propyl,n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl, iso-pentyl,sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl,iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, n-nonyl, n-decyl,and n-dodecyl; preferably C₁-C₆ alkyl such as methyl, ethyl, n-propyl,iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, n-pentyl,iso-pentyl, sec-pentyl, neo-pentyl, 1,2-dimethylpropyl, iso-amyl,n-hexyl, iso-hexyl, sec-hexyl; methyl is particularly preferred;

[0133] C₃-C₁₂ cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl,cycloundecyl and cyclododecyl; preference is given to cyclopentyl,cyclohexyl and cycloheptyl;

[0134] C₇ to C₂₀ aralkyl, preferably C₇ to C₁₂ phenylalkyl such asbenzyl, 1-phenethyl, 2-phenethyl, 1-phenylpropyl, 2-phenylpropyl,3-phenylpropyl, 1-phenylbutyl, 2-phenylbutyl, 3-phenylbutyl and4-phenylbutyl, with particular preference benzyl, or

[0135] C₆-C₁₄ aryl such as phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl,2-anthryl, 9-anthryl, 1-phenanthryl, 2-phenanthryl, 3-phenanthryl,4-phenanthryl and 9-phenanthryl, preferably phenyl, 1-naphthyl and2-naphthyl, with particular preference phenyl; and

[0136] n is an integer from 0 to 40, preferably from 1 to 25, and withparticular preference from 2 to 22.

[0137] In the literature, cagelike structures are also discussed foraluminoxanes (Y. Koide, S. G. Bott, A. R. Barron Organometallics 1996,15, 2213-26; A. R. Barron Macromol. Symp. 1995, 97, 15-25).

[0138] Irrespective of the actual structure of the aluminoxanes, theyare suitable activators for complexes of transition metals of theformulae I a to c.

[0139] Mixtures of different aluminoxanes are particularly preferredactivators in those cases where polymerization is conducted in asolution of a paraffin, n-heptane or isododecane, for example. Oneparticularly preferred mixture is the CoMAO available commercially fromWitco GmbH, having a formula of [(CH₃)_(0.9)(iso-C₄H₉)_(0.1)AlO]_(n).

[0140] To activate the complexes of the formula I a to c withaluminoxanes, it is generally necessary to use an excess of aluminoxane,based on M. Sensible M:Al molar ratios are situated within the rangefrom 1:10 to 1:10 000, preferably from 1:50 to 1:1000, and withparticular preference from 1:100 to 1:500.

[0141] The chosen complex of the formulae I a to c and thecation-forming compound together form a catalyst system. By adding oneor more further aluminum alkyl compounds of the formula Al(R²³)₃ it ispossible to increase further the activity of this catalyst system.

[0142] By adding further aluminum alkyl of the formula Al(R²³)₃ oraluminoxanes it is possible to increase the activity of the catalystsystem; aluminum alkyls of the formula Al(R²³)₃ or aluminoxanes may alsoact as molecular mass regulators. Another effective molecular massregulator is hydrogen. The molecular mass may be regulated withparticular effect by the reaction temperature and the residence time.

[0143] Modern large-scale industrial preparation processes forpolyolefin waxes are solution processes, suspension processes, bulkpolymerization processes in liquid or supercritical monomer, and gasphase processes, the latter being either stirred gas phase or gas-phasefluidized bed processes.

[0144] In order that the complexes of the formulae I a to c may be usedin suspension processes, bulk polymerization processes or gas phaseprocesses, it is advantageous to immobilize them on a solid support.Otherwise, morphological problems of the polymer (crumbs, wall deposits,blockages in pipes or heat exchangers) may occur, forcing shutdown ofthe plant.

[0145] Catalyst systems comprising complexes of the formulae I a to cand activator may be effectively deposited on a solid support. Examplesof suitable support materials are porous metal oxides, of metals fromgroups 2-14 or mixtures thereof, and also sheet silicates, and alsosolid halides of metals from groups 1, 2 and 13, and polymers such as,for example, polyethylene or polypropylene. Preferred examples of metaloxides from groups 2-14 are SiO₂, B₂O₃, Al₂O₃, MgO, CaO and ZnO.Preferred sheet silicates are montmorillonites or bentonites; preferredhalides are MgCl₂ or amorphous AlF₃.

[0146] Particularly preferred support materials are spherical silicagels and alumosilicate gels of the formula SiO₂.a Al₂O₃, where a isgenerally a number in the range from 0 to 2, preferably from 0 to 0.5.Silica gels of this kind are available commercially, e.g., Silica Gel332, Sylopol® 948 or Sylopol 952 or S 2101 from W. R. Grace or ES70×from Crosfield.

[0147] Proven particle sizes for the support material comprise averageparticle diameters of 1-300 μm, preferably from 20 to 80 μm, theparticle diameter being determined by means of known methods such assieve methods. The pore volume of these supports is from 1.0 to 3.0ml/g, preferably from 1.6 to 2.2 ml/g, and with particular preferencefrom 1.7 to 1.9 ml/g. The BET surface area is from 200 to 750 m²/g,preferably from 250 to 400 m²/g.

[0148] In order to remove impurities, especially moisture, adhering tothe support material, the support materials may be heated out prior todoping, suitable temperatures being from 45 to 1000° C. Temperatures offrom 100 to 750° C. are particularly suitable for silica gels and othermetal oxides; for MgCl₂ supports, temperature ranges from 50 to 100° C.are preferred. This heating out should take place over a period of from0.5 to 24 hours, heatout times of from 1 to 12 hours being preferred.The pressure conditions are not critical per se; heating out may takeplace under atmospheric pressure. Advantageously, however, use is madeof reduced pressures of from 0.1 to 500 mbar; a particularlyadvantageous range is from 1 to 100 mbar and a very particularlyadvantageous range from 2 to 20 mbar. Chemical pretreatment of thesupport material is another possibility.

[0149] The general procedure for doping the catalyst is to slurry thesupport material in a suspension medium and to combine this suspensionwith the solution of a complex of the formula I a to c and of theactivator. The volume of the suspension medium is from 1 to 20 times thepore volume of the catalyst support. Subsequently, the catalyst may beseparated from the suspension medium by means of an appropriate method,such as filtration, centrifugation or evaporation.

[0150] For better control of the morphology, the catalyst may beprepolymerized with small amounts of monomer prior to the polymerizationproper. The prepolymerization can be terminated by adding a reversiblecatalyst poison or by ending the feed of monomer, and the prepolymerizedcatalyst may subsequently be added to the polymerization unit.

[0151] Suitable monomers include the following olefins: ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene or1-undecene, ethylene being particularly preferred.

[0152] Suitable comonomers include α-olefins, such as from 0.1 to 20 mol% of 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene,1-decene or 1-undecene. Isobutene, however, is also a suitablecomonomer.

[0153] In order to prevent the electrostatic charging of thepolymerization unit or of the product that is occasionally observed withpolymerizations, an antistat may be added to the reaction mixture.Suitable antistats are dilute solutions of aliphatic alcohols, such asisopropanol, in paraffins such as n-heptane, for example. Furthersuitable antistats are available commercially as Stadis® products fromDuPont.

[0154] In order to prepare the paints and printing inks of theinvention, the wax, which in large-scale industrial plants is usuallyobtained in the form of a coarse powder, is micronized in a subsequentstep. Micronization is carried out using mills, an example being air jetmills. As a result of micronization, the wax is obtained as what isknown as micropowder, the maximum particle diameter not exceeding 30 μmand preferably not exceeding 25 μm.

[0155] The conventional principal constituents of the paint or printingink of the invention, in the amounts prescribed by the formulation, arefirst of all mixed with the micronized wax in high-speed stirrers knownas dissolvers. Subsequently they are mixed further, for example, instirred ball mills with a friction gap, which have been charged withgrinding beads having a diameter of from 0.05 to 5 mm, preferably from0.5 to 2.5 mm, and with particular preference 2 mm. Thereafter, thepaint or ink of the invention is passed optionally through a triple-rollmill in order to remove the oxygen incorporated by stirring.Alternatively, the printing ink may also be degassed by application of avacuum.

[0156] The weight fraction of the wax in the printing inks and paints ofthe invention is from 0.05 to 65% by weight, preferably from 0.1 to 10%by weight, and with particular preference from 0.5 to 3% by weight. Theweight fraction of the wax in the copier toners of the invention is, forexample, from 45 to 65% by weight.

[0157] Further components of the printing inks of the invention are from5 to 30% by weight of an organic or inorganic pigment, organic pigmentsbeing preferred; and also from 65 to 90% by weight of binder, comprisinga resin and, optionally, one or more solvents such as ethanol, methanol,isopropanol, water, toluene or low molecular mass hydrocarbons, forexample, and also optionally oils and antioxidants.

[0158] The printing inks of the invention are notable for particularmechanical stability, especially abrasion resistance, and for particulargloss.

WORKING EXAMPLE

[0159] Preparation of the complex (n-C₁₂H₂₅NCH₂)₃CrCl₃ andpolymerization of ethylene are described fundamentally in DE-A 199 35407, in PCT/EP 0002716, and in Angew. Chem. Int. Ed. 1994, Vol. 33, p.1877. The preparation of offset printing inks is described, for example,in the product brochure “Luwax® Poligen® Waxes and Dispersions—Use inPrinting Inks”, fundamentally, dating from 1992.

[0160] The scuff resistance was determined in a Prufbau-Quartant scufftester, while for measuring the gloss a multiangle reflectometer“Multigloss” from Byk-Chemie was used.

[0161] In a 10 liter steel autoclave (from Buchi), 50 mg (67 mmol) of(n-C₁₂H₂₅NCH₂)₃CrCl₃, dissolved in toluene, were activated with 14 ml of30% MAO from Witco, the Al:Cr ratio set being 1000:1. 4 l of isobutaneand 80 l (3.8 mol) of hydrogen were injected, and the autoclave was thenheated to 90° C. Subsequently, 40 bar of ethylene were injected andpolymerization was conducted for 30 minutes, the pressure beingmaintained at 40 bar by adding further ethylene.

[0162] The polymerization was terminated by letting down the autoclave.

[0163] Yield: 460 g, corresponding to an activity of 14,000 kg of PE(molCr·h).

[0164] The wax thus obtained had the following properties: melting point128.5° C.; M_(w): 5200 g, M_(n): 2100 g. M_(w)/M_(n)=2.5.

[0165] Number of vinyl and vinylidene double bonds/1000 carbon atoms:from 0.5 to 2.3

[0166] The wax was micronized in an opposed-jet mill until it had adiameter of 9 μm (median), determined by laser diffraction using aCoulter counter.

Example 1

[0167] 1.0% by weight of wax was dispersed in a hydrocarbon (toluene)and then incorporated into an offset printing ink Novaboard cyan 4 C 86from K+E Druckfarben (wax-free), comprising 18% by weight organicpigment, 31% by weight rosin, 34% by weight glue resin and 16% by weightmineral oil.

[0168] For the comparative examples, the following waxes wereincorporated analogously into the offset printing ink and tested.

[0169] V1: Luwax® AF 30, BASF Aktiengesellschaft, prepared byhigh-pressure polymerization

[0170] V2: Clariant Wachs PE 520® prepared by Ziegler-Natta catalysis

[0171] V3: Polyethylene wax, prepared by metallocene catalysis inaccordance with EP-A 0 890 619, example 3

[0172] For testing the abrasion resistance, a sample print was madeusing a multipurpose test bed printing machine from Dr. Dürner on paperof type Phoenomatt 115 g/m² (Scheufelen GmbH & Co. KG). The scuffingbehavior was investigated on a scuffing tester from ScheuerprüferPrüfbau Quartett), setting a scuffing load of 48 g/cm² and a scuffingspeed of 15 cm/s. Assessment was made of the intensity of the colortransferred to the test sheet through a determination of the colordifference in accordance with DIN 6174, a relatively low colordifference value indicating advantageous properties. TABLE 1 ResultsColor difference after Particle diameter Experiment 200 strokes d₅₀ [μm]1 1.9 8.9 V1 3.9 8.7 V2 3.2 9.1 V3 2.2 9.0 No wax 15.9 —

1. A printing ink or paint comprising a polyolefin wax componentprepared from one or more olefins by catalysis with a single-sitecatalyst based on a complex of the formulae I a to I c,

where the variables are defined as follows: M is an element from thegroup consisting of V, Nb, Ta, Cr, Mo, W, Mn, Fe in oxidation state +3;X¹ to X⁵ are selected from halogen, trifluoroacetate, BF₄—, PF₆— orSbF₆—, C₁—C₁₈ alkyl, C₃-C₁₂ cycloalkyl, C₇ to C₂₀ aralkyl, C₆-C₁₄ aryl,C₁-C₁₂ alkoxy, NR⁸R⁹, where R⁸ and R⁹ independently of one another areselected from hydrogen, C₁-C₁₂ alkyl, C₂-C₁₂ alkenyl and C₆-C₁₄ aryl,which are able to form a saturated or unsaturated 5- to 10-memberedring; R¹ to R⁶, Z¹ to Z⁴, R¹⁴ to R¹⁶ independently of one another areselected from hydrogen, halogen, C₁-C₁₈ alkyl, C₁-C₁₂ alkyl substitutedone or more times by donor atoms, mono- or polyhalogenated C₁-C₁₂ alkylgroups, C₂-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₇ to C₂₀ aralkyl, C₆-C₁₄aryl, silyl SiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one anotherare selected from hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄aryl; siloxy OSiR¹⁰R¹¹R¹², C₁-C₁₂ alkoxy, C₆-C₁₄ aryl, substituted inturn by one or more C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl,C₆-C₁₄ aryl, silyl SiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxygroups; where two adjacent radicals may together with one another andincluding the parent aromatic in formula I a or I b form a 5- to10-membered ring; R¹⁷ to R²² independently of one another are selectedfrom hydrogen, C₁-C₁₈ alkyl, C₁-C₂ alkyl substituted one or more timesby donor atoms, mono- or polyhalogenated C₁-C₁₂ alkyl groups, C₂-C₁₂alkenyl, C₃-C₁₂ cycloalkyl, C₇ to C₂₀ aralkyl, C₆-C₁₄ aryl, silylSiR¹⁰R¹¹R¹², where R¹⁰ to R¹² independently of one another are selectedfrom hydrogen, C₁-C₁₂ alkyl, C₇-C₁₅ aralkyl and C₆-C₁₄ aryl; siloxyOSiR¹⁰R¹¹R¹², C₁-C₁₂ alkoxy, C₆-C₁₄ aryl substituted in turn by one ormore C₁-C₁₂ alkyl, C₁-C₁₂ alkenyl, C₃-C₁₂ cycloalkyl, C₆-C₁₄ aryl, silylSiR¹⁰R¹¹R¹², siloxy OSiR¹⁰R¹¹R¹² or C₁-C₁₂ alkoxy groups; where twoadjacent radicals R¹⁴ to R²² in formula I c may together form asaturated or unsaturated 4- to 9-membered ring; A¹ is O—R³, S—R¹³,N—(R¹³)₂ or P—(R¹³)₂, R¹³ being selected from halogen, C₁-C₁₂ alkyl,C₃-C₁₂ cycloalkyl, substituted or unsubstituted C₆-C₁₄aryl groups orC₁-C₁₂ alkoxy groups, these groups being as defined for R¹ to R⁶; A² isoxygen, sulfur, N—R¹³ or P—R¹³, R¹³ being selected from halogen, C₁-C₁₂alkyl, C₃-C₁₂ cycloalkyl, substituted or unsubstituted C₆-C₁₄ arylgroups or C₁-C₁₂ alkoxy groups, these groups being as defined for R¹ toR⁶; where Z⁴ and A² in formula I b may together with one another andincluding the phenyl ring in formula I b form a 5- to 10-membered ring;Nu¹ to Nu³ are each N or P.
 2. A printing ink or paint as claimed inclaim 1, wherein the polyolefin wax is prepared by catalysis with asingle-site catalyst based on a tri-pnicogen-cyclohexane complex of theformula I c.
 3. A printing ink or paint as claimed in claim 1, whereinthe polyolefin wax is prepared by catalysis with a single-site catalystbased on a 1,3,5-triazacyclohexane complex, a1,3-diaza-5-phosphacyclohexane complex or a 1,3,5-triphosphacyclohexanecomplex of the formula I c.
 4. A printing ink or paint as claimed inclaim 1, wherein the polyolefin wax is prepared by catalysis with asingle-site catalyst based on a Cr complex of the formula I c.
 5. Theuse of micronized particles of polyolefin waxes prepared as in claim 1to prepare printing inks and paints.
 6. A process for preparing printinginks and paints, which comprises using micronized polyolefin waxparticles based on polyolefin waxes prepared as in claim
 1. 7. A methodof printing paper or cardboard, which comprises using a printing ink asclaimed in claim 1.